JP2016050364A - Copper foil with carrier, copper-clad laminate, printed wiring board, electronic device, laminate, method for producing copper foil with carrier, method for producing copper-clad laminate, and method for producing printed wiring board - Google Patents

Abstract

Provided is a copper foil with a carrier in which the change in the peel strength of the carrier before and after the hot pressing of the copper foil with a carrier is satisfactorily suppressed.
A copper foil with a carrier provided with a carrier, an intermediate layer, and an ultrathin copper layer in this order, and the copper foil with a carrier is subjected to pressure: 20 kgf / cm ² at 220 ° C. for 2 hours. The peel strength of the carrier after being hot pressed at 150 ° C. or less is 150% or less of the peel strength before the hot press, and the carrier is peeled after being hot pressed under the conditions of pressure: 20 kgf / cm ² and 220 ° C. for 2 hours. A copper foil with a carrier having a strength of 2 N / m to 30 N / m.
[Selection] Figure 1

Description

  The present invention relates to a copper foil with a carrier, a copper clad laminate, a printed wiring board, an electronic device, a laminate, a method for producing a copper foil with a carrier, a method for producing a copper clad laminate, and a method for producing a printed wiring board.

  Generally, a printed wiring board is manufactured through a process in which an insulating substrate is bonded to a copper foil to form a copper-clad laminate, and then a conductor pattern is formed on the copper foil surface by etching. In recent years, with the increasing needs for miniaturization and higher performance of electronic devices, higher density mounting of components and higher frequency of signals have progressed, and conductor patterns have become finer (fine pitch) and higher frequency than printed circuit boards. Response is required.

  Recently, copper foils with a thickness of 9 μm or less and further with a thickness of 5 μm or less have been required in response to the fine pitch, but such ultra-thin copper foils have low mechanical strength and are used in the manufacture of printed wiring boards. Copper foil with a carrier has appeared, in which a thick metal foil is used as a carrier, and an ultrathin copper layer is electrodeposited through a release layer, since it is easily broken or wrinkled. After bonding the surface of the ultrathin copper layer to an insulating substrate and thermocompression bonding, the carrier is peeled and removed through the peeling layer. After a circuit pattern is formed with a resist on the exposed ultrathin copper layer, a predetermined circuit is formed (Patent Document 1, etc.).

WO2004 / 005588

  As described above, the carrier-attached copper foil is used after the surface of the ultrathin copper layer is bonded to an insulating substrate and thermocompression bonded (heat press), and then the carrier is peeled off. The carrier peel strength at this time is preferably the strength desired by the user. However, the peel strength of the carrier that is adjusted at the stage of manufacturing the copper foil with carrier is lowered or increased after the heat press with the insulating substrate, and the user who uses the copper foil with carrier attached to the insulating substrate is used. However, the desired carrier peel strength cannot be obtained. When such a desired peel strength cannot be obtained, when the carrier is peeled and removed from the carrier-attached copper foil bonded to the insulating substrate, the peel becomes difficult and the yield decreases, or the peel is impossible. There is a problem that wrinkles are generated in the ultrathin copper layer due to the force, or the carrier is peeled off during the manufacturing process of the printed wiring board or the like.

  Then, this invention makes it a subject to provide the copper foil with a carrier by which the change of the peeling strength of a carrier was suppressed favorably before and behind the hot press of the copper foil with a carrier.

The present invention has been completed on the basis of the above knowledge, and in one aspect, a carrier-attached copper foil comprising a carrier, an intermediate layer, and an ultrathin copper layer in this order, the carrier-attached copper foil, Pressure: 20 kgf / cm ² , the carrier peel strength after heat pressing at 220 ° C. for 2 hours is 150% or less of the peel strength before the heat press, pressure: 20 kgf / cm ² , 220 It is a copper foil with a carrier whose peeling strength of the said carrier after heat-pressing on conditions of 2 degreeC at 2 degreeC is 2 N / m or more and 30 N / m or less. Further, the peel strength of the carrier after heat-pressing the copper foil with carrier under the conditions of pressure: 20 kgf / cm ² and 220 ° C. for 2 hours is 150% or less of the peel strength before the heat press. , Pressure: 20 kgf / cm ² , the carrier peel strength after heat pressing at 220 ° C. for 2 hours is 5 N / m to 30 N / m, 5 N / m to 25 N / m, or 5 N / M or more and 20 N / m or less is preferable.

In one embodiment of the copper foil with a carrier of the present invention, the peel strength of the carrier after the copper foil with a carrier is heated and pressed under the conditions of pressure: 20 kgf / cm ² and 220 ° C. for 2 hours is It is 50 to 150% of the peel strength before pressing.

  In another embodiment of the copper foil with a carrier of the present invention, the thickness of the carrier is 5 to 70 μm.

  In yet another embodiment, the carrier-attached copper foil of the present invention has a roughened layer on one or both of the ultrathin copper layer side surface and the carrier side surface.

  In another embodiment of the copper foil with a carrier of the present invention, the roughening treatment layer is selected from the group consisting of copper, nickel, phosphorus, tungsten, arsenic, molybdenum, chromium, iron, vanadium, cobalt, and zinc. It is a layer made of any single substance or an alloy containing one or more kinds.

  In yet another embodiment, the carrier-attached copper foil of the present invention is one type selected from the group consisting of a heat-resistant layer, a rust-proof layer, a chromate-treated layer, and a silane coupling-treated layer on the surface of the roughened layer. It has the above layers.

  In yet another embodiment, the carrier-attached copper foil of the present invention is one type selected from the group consisting of a heat-resistant layer, a rust-proof layer, a chromate treatment layer, and a silane coupling treatment layer on the surface of the ultrathin copper layer. It has the above layers.

  In still another embodiment, the carrier-attached copper foil of the present invention includes a resin layer on the ultrathin copper layer.

  In yet another embodiment, the carrier-attached copper foil of the present invention includes a resin layer on the roughening treatment layer.

  In yet another embodiment, the carrier-attached copper foil of the present invention is a resin layer on one or more layers selected from the group consisting of the heat-resistant layer, the rust-proof layer, the chromate-treated layer, and the silane coupling-treated layer. Is provided.

  In another embodiment, the copper foil with a carrier of the present invention has an intermediate layer and an ultrathin copper layer in this order on both sides of the carrier.

  In yet another aspect, the present invention is a copper clad laminate made of the carrier-attached copper foil of the present invention.

  In yet another aspect, the present invention is a printed wiring board made of the carrier-attached copper foil of the present invention.

  In still another aspect, the present invention is an electronic device having the printed wiring board of the present invention.

  In still another aspect, the present invention is a laminate using the carrier-attached copper foil of the present invention as a material.

  According to still another aspect of the present invention, there is provided a laminate including the carrier-attached copper foil of the present invention and a resin, wherein the end face of the carrier-attached copper foil is partially or entirely covered with the resin. It is.

  In yet another aspect of the present invention, the carrier-attached copper foil of the present invention is separated from the carrier side or the ultrathin copper layer side of the present invention, and the carrier-side copper foil of the present invention of the other is provided. It is the laminated body laminated | stacked on the copper layer side.

  In one embodiment of the laminate of the present invention, the carrier-side surface or ultrathin copper layer side surface of the one carrier-attached copper foil and the carrier-side surface or ultrathin copper of the another carrier-attached copper foil. The layer-side surface is configured to be directly laminated through an adhesive as necessary.

  In another embodiment of the laminate of the present invention, the carrier or the ultrathin copper layer of the one carrier-attached copper foil and the carrier or the ultrathin copper layer of the other carrier-attached copper foil are joined. Has been.

  In another embodiment of the laminate of the present invention, part or all of the end face of the laminate is covered with a resin.

  In yet another aspect of the present invention, the carrier-attached copper foil provided with the carrier, the intermediate layer, and the ultrathin copper layer in this order is subjected to an annealing treatment at 160 to 220 ° C. for 5 minutes to 5 hours. It is a manufacturing method of the copper foil with a carrier containing this.

  In one embodiment of the method for producing a copper foil with a carrier of the present invention, the annealing treatment is performed at 170 to 190 ° C. for 1 to 2 hours.

  In still another aspect, the present invention is a method for producing a copper-clad laminate including a step of bonding an insulating substrate and a copper foil with a carrier produced by the method for producing a copper foil with a carrier of the present invention.

In another aspect of the present invention, a step of preparing the carrier-attached copper foil of the present invention and an insulating substrate,
A step of laminating the copper foil with carrier and an insulating substrate; and
After laminating the carrier-attached copper foil and the insulating substrate, forming a copper-clad laminate through a step of peeling the carrier of the carrier-attached copper foil,
Thereafter, the printed wiring board manufacturing method includes a step of forming a circuit by any one of a semi-additive method, a subtractive method, a partly additive method, or a modified semi-additive method.

In another aspect of the present invention, a step of forming a circuit on the ultrathin copper layer side surface or the carrier side surface of the carrier-attached copper foil of the present invention,
Forming a resin layer on the ultrathin copper layer side surface or the carrier side surface of the copper foil with carrier so that the circuit is buried;
After forming the resin layer, the step of peeling the carrier or the ultrathin copper layer, and
After the carrier or the ultra-thin copper layer is peeled off, the ultra-thin copper layer or the carrier is removed to be buried in the resin layer formed on the ultra-thin copper layer-side surface or the carrier-side surface. It is a manufacturing method of a printed wiring board including the process of exposing the circuit which has been carried out.

In another aspect of the present invention, a step of forming a circuit on the ultrathin copper layer side surface or the carrier side surface of the carrier-attached copper foil of the present invention,
Forming a resin layer on the ultrathin copper layer side surface or the carrier side surface of the copper foil with carrier so that the circuit is buried;
Forming a circuit on the resin layer;
After forming a circuit on the resin layer, peeling the carrier or the ultra-thin copper layer; and
After the carrier or the ultra-thin copper layer is peeled off, the ultra-thin copper layer or the carrier is removed to be buried in the resin layer formed on the ultra-thin copper layer-side surface or the carrier-side surface. It is a manufacturing method of a printed wiring board including the process of exposing the circuit which has been carried out.

In another aspect of the present invention, the step of laminating the ultrathin copper layer side surface or the carrier side surface of the copper foil with carrier of the present invention and a resin substrate,
A step of providing at least once two layers of a resin layer and a circuit on the surface of the ultrathin copper layer on the side opposite to the side laminated with the resin substrate of the copper foil with carrier or on the surface of the carrier; and
It is a manufacturing method of a printed wiring board including the process of exfoliating the carrier or the ultra-thin copper layer from the copper foil with a carrier after forming the resin layer and the two layers of the circuit.

In yet another aspect of the present invention, the step of laminating the carrier-side surface of the copper foil with a carrier of the present invention and a resin substrate,
A step of providing two layers of a resin layer and a circuit at least once on the surface of the ultrathin copper layer side opposite to the side laminated with the resin substrate of the copper foil with carrier, and
It is a manufacturing method of a printed wiring board including the process of exfoliating the ultra-thin copper layer from the copper foil with a carrier after forming the resin layer and two layers of a circuit.

  ADVANTAGE OF THE INVENTION According to this invention, the copper foil with a carrier in which the change of the peeling strength of a carrier before and behind the hot press of the copper foil with a carrier was suppressed favorably can be provided.

AC is a schematic diagram of the wiring board cross section in the process to circuit plating and the resist removal based on the specific example of the manufacturing method of the printed wiring board using the copper foil with a carrier of this invention. DF is a schematic diagram of a cross section of a wiring board in a process from lamination of a resin and copper foil with a second layer carrier to laser drilling according to a specific example of a method for producing a printed wiring board using a copper foil with a carrier of the present invention. It is. GI is a schematic diagram of the wiring board cross section in the process from the via fill formation to the first layer carrier peeling according to a specific example of the method for manufacturing a printed wiring board using the carrier-attached copper foil of the present invention. J to K are schematic views of a cross section of a wiring board in steps from flash etching to bump / copper pillar formation according to a specific example of a method of manufacturing a printed wiring board using the carrier-attached copper foil of the present invention. It is a schematic diagram which shows the measurement location of the sample sheet which concerns on an Example.

<Copper foil with carrier>
The copper foil with a carrier of the present invention includes a carrier, an intermediate layer laminated on the carrier, and an ultrathin copper layer laminated on the intermediate layer. The method of using the copper foil with carrier itself is well known to those skilled in the art. For example, the surface of the ultra-thin copper layer is made of paper base phenol resin, paper base epoxy resin, synthetic fiber cloth base epoxy resin, glass cloth / paper composite. Ultra-thin bonded to an insulating substrate, bonded to an insulating substrate such as a base epoxy resin, glass cloth / glass nonwoven fabric composite epoxy resin and glass cloth base epoxy resin, polyester film, polyimide film, etc. The copper layer can be etched into the intended conductor pattern to finally produce a printed wiring board.

In the carrier-attached copper foil of the present invention, the peel strength of the carrier after being hot-pressed under the conditions of pressure: 20 kgf / cm ² and 220 ° C. for 2 hours is 150% or less of the peel strength before the heat-press. According to such a structure, the change of the peeling strength of the carrier before and after the hot pressing of the copper foil with a carrier can be satisfactorily suppressed. It is considered that the peel strength does not change so much in the subsequent heat treatment such as heating press because the interdiffusion of atoms between the carrier, the intermediate layer, and the ultrathin copper layer is appropriately performed by performing the predetermined heating. . Also, the carrier peel strength after heat-pressing the copper foil with carrier under the conditions of pressure: 20 kgf / cm ² and 220 ° C. for 2 hours is 50 to 150% of the peel strength before the heat press. Preferably, it is 60 to 140%, more preferably 70 to 135%, still more preferably 80 to 120%, and still more preferably 90 to 110%. The above “pressure: 20 kgf / cm ² , heat-pressed at 220 ° C. for 2 hours” shows typical heat-press conditions when a carrier-attached copper foil is bonded to an insulating substrate and thermocompression bonded. Yes.

Control of the peeling strength of the carrier after the hot pressing of the copper foil with a carrier is realized by the following manufacturing method. That is, a carrier-attached copper foil provided with a carrier, an intermediate layer, and an ultrathin copper layer in this order is prepared. Next, the copper foil with a carrier is annealed at 160 to 220 ° C. for 5 minutes to 5 hours. In this way, by performing a predetermined annealing treatment on the copper foil with a carrier, the peel strength of the carrier after being hot-pressed under the conditions of pressure: 20 kgf / cm ² and 220 ° C. for 2 hours is determined before the heat-press. The strength can be controlled to 150% or less, and the peel strength of the carrier after being heat-pressed under the conditions of pressure: 20 kgf / cm ² and 220 ° C. for 2 hours may be 2 N / m or more and 30 N / m or less. it can. And the copper foil with a carrier that satisfies the conditions does not change much in the peel strength of the carrier due to the hot press, and the peel strength of the carrier is in a predetermined range. For example, due to the heat load at the time of manufacturing the multilayer printed wiring board Since it is difficult for the carrier to be peeled off or the problem that the carrier is peeled off, it is effective because productivity at the time of manufacturing a printed wiring board is improved. Under the above annealing conditions, if the heating temperature is less than 160 ° C. or the heating time is less than 5 minutes, the peel strength after hot pressing may not be controlled. On the other hand, if the heating temperature exceeds 220 ° C. or the heating time exceeds 5 hours, the peel strength after heating becomes too high, and it may not be possible to control the peel strength before heating press to 150% or less. The annealing treatment is preferably performed at 170 to 190 ° C for 1 to 2 hours, more preferably at 175 to 190 ° C for 1 to 2 hours, and at 175 to 185 ° C for 1 to 2 hours. It is more preferable to carry out under conditions.

Further, the peel strength of the carrier after heat-pressing the copper foil with carrier under the conditions of pressure: 20 kgf / cm ² and 220 ° C. for 2 hours is 150% or less of the peel strength before the heat press. , Pressure: 20 kgf / cm ^{2 It} is preferable that the peel strength of the carrier after heat pressing at 220 ° C. for 2 hours is 5 N / m or more and 30 N / m or less. According to such a configuration, the carrier is not peeled off during the printed wiring board manufacturing process, and is easily peeled off when it is necessary to peel off. Therefore, the yield and work efficiency of the printed wiring board manufacturing process are improved. The peel strength of the carrier is more preferably 5 N / m or more and 25 N / m or less, and still more preferably 5 N / m or more and 20 N / m or less.

<Career>
Carriers that can be used in the present invention are typically metal foils or resin films, such as copper foil, copper alloy foil, nickel foil, nickel alloy foil, iron foil, iron alloy foil, stainless steel foil, aluminum foil, aluminum. It is provided in the form of alloy foil, insulating resin film, polyimide film, and LCP film.
Carriers that can be used in the present invention are typically provided in the form of rolled copper foil or electrolytic copper foil. In general, the electrolytic copper foil is produced by electrolytic deposition of copper from a copper sulfate plating bath onto a titanium or stainless steel drum, and the rolled copper foil is produced by repeating plastic working and heat treatment with a rolling roll. Examples of copper foil materials include high-purity copper such as tough pitch copper (JIS H3100 alloy number C1100) and oxygen-free copper (JIS H3100 alloy number C1020 or JIS H3510 alloy number C1011), for example, Sn-containing copper, Ag-containing copper, Cr A copper alloy such as a copper alloy added with Zr or Mg, or a Corson copper alloy added with Ni, Si or the like can also be used.
Moreover, as electrolytic copper foil, it can produce with the following electrolyte solution composition and manufacturing conditions.
In addition, the remainder of the process liquid used for manufacture of the copper foil described in this specification, surface treatment of copper foil, plating of copper foil, etc. is water unless otherwise specified.
<Electrolytic solution composition>
Copper: 90-110 g / L
Sulfuric acid: 90-110 g / L
Chlorine: 50-100ppm
Leveling agent 1 (bis (3sulfopropyl) disulfide): 10 to 30 ppm
Leveling agent 2 (amine compound): 10 to 30 ppm
As the amine compound, an amine compound having the following chemical formula can be used.

(In the above chemical formula, R ₁ and R ₂ are selected from the group consisting of a hydroxyalkyl group, an ether group, an aryl group, an aromatic substituted alkyl group, an unsaturated hydrocarbon group, and an alkyl group.)

<Production conditions>
Current density: 70 to 100 A / dm ²
Electrolyte temperature: 50-60 ° C
Electrolyte linear velocity: 3-5 m / sec
Electrolysis time: 0.5 to 10 minutes In addition, when the term “copper foil” is used alone in this specification, a copper alloy foil is also included.

  The thickness of the carrier that can be used in the present invention is not particularly limited, but may be appropriately adjusted to a thickness suitable for serving as a carrier, and may be, for example, 5 μm or more and 70 μm or less. However, if it is too thick, the production cost becomes high, so generally it is preferably 35 μm or less. The thickness of the carrier is typically 8 μm or more and 70 μm or less, more typically 12 μm or more and 70 μm or less, and more typically 18 μm or more and 35 μm or less. Moreover, it is preferable that the thickness of a carrier is small from a viewpoint of reducing raw material cost. Therefore, the thickness of the carrier is typically 5 μm or more and 35 μm or less, preferably 5 μm or more and 18 μm or less, preferably 5 μm or more and 12 μm or less, preferably 5 μm or more and 11 μm or less, preferably 5 μm or more and 10 μm or less. It is as follows. In addition, when the thickness of a carrier is small, it is easy to generate | occur | produce a wrinkle in the case of a carrier foil. In order to prevent the generation of folding wrinkles, for example, it is effective to smooth the transport roll of the copper foil manufacturing apparatus with a carrier and to shorten the distance between the transport roll and the next transport roll. In addition, when the copper foil with a carrier is used for the embedding method (embedded process) which is one of the manufacturing methods of a printed wiring board, the rigidity of a carrier needs to be high. Therefore, when used in the embedding method, the thickness of the carrier is preferably 18 μm or more and 300 μm or less, preferably 25 μm or more and 150 μm or less, preferably 35 μm or more and 100 μm or less, and 35 μm or more and 70 μm or less. Even more preferred.

<Intermediate layer>
An intermediate layer is provided on the carrier. Another layer may be provided between the carrier and the intermediate layer. In the intermediate layer used in the present invention, the ultrathin copper layer is hardly peeled off from the carrier before the copper foil with the carrier is laminated on the insulating substrate, while the ultrathin copper layer is separated from the carrier after the lamination step on the insulating substrate. There is no particular limitation as long as it can be peeled off. For example, the intermediate layer of the copper foil with a carrier of the present invention is Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, alloys thereof, hydrates thereof, oxides thereof, One or two or more selected from the group consisting of organic substances may be included. The intermediate layer may be a plurality of layers. Further, an intermediate layer and an ultrathin copper layer may be provided in this order on both sides of the carrier.

  Further, for example, the intermediate layer is a single metal layer composed of one kind of element selected from the element group composed of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn from the carrier side. Or forming an alloy layer composed of one or more elements selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, Zn, A layer made of a hydrate or oxide of one or more elements selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al, and Zn. It can comprise by forming. The intermediate layer preferably contains the aforementioned metal element. This is because when the intermediate layer is composed only of organic substances, the peel strength after pressing may be reduced.

  An intermediate layer containing Ni can be provided on one or both sides of the carrier. The intermediate layer is formed by laminating any one layer of nickel or an alloy containing nickel on the carrier and a layer containing any one or more of chromium, a chromium alloy, and an oxide of chromium in this order. It is preferable. In addition, it is preferable that zinc is contained in any one layer of nickel or an alloy containing nickel and / or a layer containing any one or more of chromium, a chromium alloy, and an oxide of chromium. Here, the alloy containing nickel is composed of nickel and one or more elements selected from the group consisting of cobalt, iron, chromium, molybdenum, zinc, tantalum, copper, aluminum, phosphorus, tungsten, tin, arsenic, and titanium. An alloy. The alloy containing nickel may be an alloy composed of three or more elements. The chromium alloy is an alloy composed of chromium and one or more elements selected from the group consisting of cobalt, iron, nickel, molybdenum, zinc, tantalum, copper, aluminum, phosphorus, tungsten, tin, arsenic, and titanium. Say. The chromium alloy may be an alloy composed of three or more elements. Further, the layer containing any one or more of chromium, a chromium alloy, and a chromium oxide may be a chromate treatment layer. Here, the chromate-treated layer refers to a layer treated with a liquid containing chromic anhydride, chromic acid, dichromic acid, chromate or dichromate. Chromate treatment layer is any element such as cobalt, iron, nickel, molybdenum, zinc, tantalum, copper, aluminum, phosphorus, tungsten, tin, arsenic and titanium (metal, alloy, oxide, nitride, sulfide, etc.) May be included). Specific examples of the chromate treatment layer include a pure chromate treatment layer and a zinc chromate treatment layer. In the present invention, a chromate treatment layer treated with an anhydrous chromic acid or potassium dichromate aqueous solution is referred to as a pure chromate treatment layer. In the present invention, a chromate treatment layer treated with a treatment liquid containing chromic anhydride or potassium dichromate and zinc is referred to as a zinc chromate treatment layer.

The intermediate layer is any one of nickel, nickel-zinc alloy, nickel-phosphorus alloy and nickel-cobalt alloy on the carrier, and any of zinc chromate treatment layer, pure chromate treatment layer and chromium plating layer. It is preferable that one kind of layer is laminated in this order, and the intermediate layer is constituted by laminating a nickel layer or a nickel-zinc alloy layer and a zinc chromate treatment layer in this order on the carrier. More preferably, the nickel-zinc alloy layer and the pure chromate treatment layer or the zinc chromate treatment layer are laminated in this order. Since the adhesive force between nickel and copper is higher than the adhesive force between chromium and copper, when the ultrathin copper layer is peeled off, it peels at the interface between the ultrathin copper layer and the chromate treatment layer. Further, the nickel of the intermediate layer is expected to have a barrier effect that prevents the copper component from diffusing from the carrier into the ultrathin copper layer. Further, it is preferable to form a chromate treatment layer on the intermediate layer instead of chrome plating. Since chromium plating forms a dense chromium oxide layer on the surface, when an ultrathin copper foil is formed by electroplating, the electrical resistance increases and pinholes are likely to occur. The surface on which the chromate treatment layer is formed has a chromium oxide layer that is less dense than chrome plating, so resistance to formation of ultrathin copper foil by electroplating is less likely to reduce pinholes. it can. Here, by forming a zinc chromate treatment layer as a chromate treatment layer, the resistance when forming an ultrathin copper foil by electroplating is lower than that of a normal chromate treatment layer, and the generation of pinholes is further suppressed. be able to.
When using electrolytic copper foil as a carrier, it is preferable to provide an intermediate layer on the shiny surface from the viewpoint of reducing pinholes.

  Among the intermediate layers, the chromate treatment layer is thinly present at the interface of the ultrathin copper layer, while the ultrathin copper layer does not peel off from the carrier before the laminating process on the insulating substrate, while after the laminating process on the insulating substrate It is preferable for obtaining the property that the ultrathin copper layer can be peeled from the carrier. When the chromate treatment layer is present at the boundary between the carrier and the ultrathin copper layer without providing a nickel layer or an alloy layer containing nickel (for example, a nickel-zinc alloy layer), the peelability is hardly improved, and the chromate treatment layer If the nickel layer or the alloy layer containing nickel (for example, nickel-zinc alloy layer) and the ultrathin copper layer are directly laminated, the nickel amount in the nickel layer or the alloy layer containing nickel (for example, nickel-zinc alloy layer) Accordingly, the peel strength is too strong or too weak to obtain an appropriate peel strength.

  Further, if the chromate treatment layer is present at the boundary between the carrier and the nickel layer or nickel-containing alloy layer (for example, nickel-zinc alloy layer), the intermediate layer is also peeled along with the peeling of the ultrathin copper layer, that is, the carrier. And the intermediate layer is undesirably peeled off. Such a situation may occur not only when the chromate treatment layer is provided at the interface with the carrier, but also when the amount of chromium is excessive even if the chromate treatment layer is provided at the interface with the ultrathin copper layer. This is because copper and nickel are likely to be in solid solution, so if they are in contact with each other, the adhesive force increases due to mutual diffusion and is difficult to peel off, while chromium and copper are less likely to dissolve and cause mutual diffusion. It is considered that the adhesion between the chromium and copper interface is weak and easy to peel off. Further, when the nickel amount in the intermediate layer is insufficient, there is only a very small amount of chromium between the carrier and the ultrathin copper layer, so that they are in close contact with each other and are difficult to peel off.

The intermediate nickel layer or nickel-containing alloy layer (for example, nickel-zinc alloy layer) is formed by wet plating such as electroplating, electroless plating and immersion plating, or dry plating such as sputtering, CVD and PDV. can do. Electroplating is preferable from the viewpoint of cost. When the carrier is a resin film, the intermediate layer can be formed by dry plating such as CVD and PDV or wet plating such as electroless plating and immersion plating.
In addition, the chromate treatment layer can be formed with, for example, electrolytic chromate or immersion chromate, but the chromium concentration can be increased, and the peel strength of the ultra-thin copper layer from the carrier is improved. Preferably formed.
Note that in the case that contains the nickel intermediate layer is preferably nickel coating weight is 100~40000μg / dm ^2, preferably a 500~30000μg / dm ^2, a 800~20000μg / dm ² Is more preferable, and 900 to 15000 μg / dm ² is more preferable.
Further, it if contains a chromium intermediate layer, the chromium coating weight is preferably from 1-1000 / dm ^2, is preferably 2~800μg / dm ^2, a 3~150μg / dm ² Is preferably 4 to 100 μg / dm ² , and more preferably 5 to 50 μg / dm ² .
Incidentally, if included in the intermediate layer of molybdenum (Mo) is preferably contained 50 [mu] g / dm ² or more 1000 [mu] g / dm ² or less Mo, and more preferably contains 70 [mu] g / dm ² or more 650μg / dm ² or less.
Incidentally, if included in the intermediate layer is cobalt (Co) is preferably contained 50 [mu] g / dm ² or more 1000 [mu] g / dm ² or less Co, and more preferably contains 70 [mu] g / dm ² or more 650μg / dm ² or less.
Incidentally, if included zinc in the intermediate layer (Zn) it is is preferably contains Zn 1 [mu] g / dm ² or more 120 [mu] g / dm ² or less, more preferably containing 2 [mu] g / dm ² or more 70 [mu] g / dm ² or less, It is more preferable to contain 5 μg / dm ² or more and 50 μg / dm ² or less.

  Even if the intermediate | middle layer of the copper foil with a carrier of this invention is laminated | stacked in order of the organic layer containing either a nickel layer and a nitrogen containing organic compound, a sulfur containing organic compound, and carboxylic acid on a carrier. Good. Moreover, the intermediate layer of the copper foil with a carrier of the present invention is formed by laminating an organic material layer containing any of a nitrogen-containing organic compound, a sulfur-containing organic compound and a carboxylic acid, and a nickel layer on the carrier. May be. Moreover, BTA (benzotriazole), MBT (mercaptobenzothiazole), etc. are mentioned as an organic substance containing either the said nitrogen containing organic compound, sulfur containing organic compound, and carboxylic acid.

Moreover, as an organic substance which an intermediate | middle layer contains, it is preferable to use what consists of 1 type (s) or 2 or more types selected from a nitrogen containing organic compound, a sulfur containing organic compound, and carboxylic acid. Among the nitrogen-containing organic compound, the sulfur-containing organic compound, and the carboxylic acid, the nitrogen-containing organic compound includes a nitrogen-containing organic compound having a substituent. Specific nitrogen-containing organic compounds include 1,2,3-benzotriazole, carboxybenzotriazole, N ′, N′-bis (benzotriazolylmethyl) urea, 1H-1 which are triazole compounds having a substituent. 2,4-triazole, 3-amino-1H-1,2,4-triazole and the like are preferably used.
For the sulfur-containing organic compound, it is preferable to use mercaptobenzothiazole, 2-mercaptobenzothiazole sodium, thiocyanuric acid, 2-benzimidazolethiol, and the like.
As the carboxylic acid, it is particularly preferable to use a monocarboxylic acid, and it is particularly preferable to use oleic acid, linoleic acid, linolenic acid, or the like.
The organic material is preferably contained in a thickness of 25 nm to 80 nm, more preferably 30 nm to 70 nm. The intermediate layer may contain a plurality of types (one or more) of the aforementioned organic substances.
In addition, the thickness of organic substance can be measured as follows.

<Thickness of organic material in the intermediate layer>
After peeling off the ultrathin copper layer of the carrier-attached copper foil from the carrier, the surface of the exposed ultrathin copper layer on the intermediate layer side and the exposed surface of the intermediate layer side of the carrier are subjected to XPS measurement to create a depth profile. The depth at which the carbon concentration first becomes 3 at% or less from the surface on the intermediate layer side of the ultrathin copper layer is defined as A (nm), and the carbon concentration is initially 3 at% or less from the surface on the intermediate layer side of the carrier. The resulting depth can be defined as B (nm), and the sum of A and B can be defined as the thickness (nm) of the organic substance in the intermediate layer.
XPS operating conditions are shown below.
・ Device: XPS measuring device (ULVAC-PHI, Model 5600MC)
・ Achieving vacuum: 3.8 × 10 ⁻⁷ Pa
X-ray: Monochromatic AlKα or non-monochromatic MgKα, X-ray output 300 W, detection area 800 μmφ, angle between sample and detector 45 °
Ion beam: ion species Ar ⁺ , acceleration voltage 3 kV, sweep area 3 mm × 3 mm, sputtering rate 2.8 nm / min (in terms of SiO ₂ )

  The method for using the organic substance contained in the intermediate layer will be described below with reference to the method for forming the intermediate layer on the carrier foil. The intermediate layer is formed on the carrier by dissolving the above-mentioned organic substance in a solvent and immersing the carrier in the solvent, or showering, spraying method, dropping method and electrodeposition method on the surface on which the intermediate layer is to be formed. Etc., and there is no need to adopt a particularly limited method. At this time, the concentration of the organic agent in the solvent is preferably in the range of a concentration of 0.01 g / L to 30 g / L and a liquid temperature of 20 to 60 ° C. in all the organic substances described above. The concentration of the organic substance is not particularly limited, and there is no problem even if the concentration is originally high or low. In addition, the organic substance thickness of an intermediate | middle layer tends to become large, so that the density | concentration of organic substance is high, and the contact time of the carrier to the solvent which dissolved the organic substance mentioned above is long. And when the organic substance thickness of an intermediate | middle layer is thick, it exists in the tendency for the effect of organic substance to suppress the spreading | diffusion to the ultra-thin copper layer side of Ni to become large.

<Ultrathin copper layer>
An ultrathin copper layer is provided on the intermediate layer. Another layer may be provided between the intermediate layer and the ultrathin copper layer. The ultra-thin copper layer can be formed by electroplating using an electrolytic bath such as copper sulfate, copper pyrophosphate, copper sulfamate, copper cyanide, etc., and the copper layer can be formed at a high current density. A copper sulfate bath is preferred. The thickness of the ultrathin copper layer is not particularly limited, but is generally thinner than the carrier, for example, 12 μm or less. It is typically 0.5-12 μm, more typically 1-5 μm, even more typically 1.5-5 μm, and even more typically 2-5 μm. The ultra thin copper layer may be provided on both sides of the carrier.

<Roughening treatment and other surface treatment>
A roughening treatment layer may be provided on the surface of the ultrathin copper layer by performing a roughening treatment, for example, in order to improve the adhesion to the insulating substrate. A roughening treatment layer may be provided on one or both of the ultrathin copper layer surface and the carrier surface. The roughening treatment can be performed, for example, by forming roughened particles with copper or a copper alloy. The roughening process may be fine. The roughening treatment layer is a layer made of any single element selected from the group consisting of copper, nickel, phosphorus, tungsten, arsenic, molybdenum, chromium, iron, vanadium, cobalt, and zinc, or an alloy containing at least one of them. It may be. Moreover, after forming the roughened particles with copper or a copper alloy, a roughening treatment can be performed in which secondary particles or tertiary particles are further formed of nickel, cobalt, copper, zinc alone or an alloy. Thereafter, a heat-resistant layer or a rust-preventing layer may be formed of nickel, cobalt, copper, zinc alone or an alloy, and the surface thereof may be further subjected to a treatment such as a chromate treatment or a silane coupling treatment. Alternatively, a heat-resistant layer or a rust-preventing layer may be formed from nickel, cobalt, copper, zinc alone or an alloy without roughening, and the surface may be subjected to a treatment such as chromate treatment or silane coupling treatment. Good. That is, one or more layers selected from the group consisting of a heat-resistant layer, a rust-preventing layer, a chromate treatment layer, and a silane coupling treatment layer may be formed on the surface of the roughening treatment layer. One or more layers selected from the group consisting of a heat-resistant layer, a rust prevention layer, a chromate treatment layer, and a silane coupling treatment layer may be formed on the surface. In addition, the above-mentioned heat-resistant layer, rust prevention layer, chromate treatment layer, and silane coupling treatment layer may each be formed of a plurality of layers (for example, 2 layers or more, 3 layers or more, etc.).
Here, the chromate-treated layer may be the above-mentioned chromate-treated layer or other chromate-treated layer.

As the heat-resistant layer and the rust-proof layer, known heat-resistant layers and rust-proof layers can be used. For example, the heat-resistant layer and / or the anticorrosive layer is a group of nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, platinum group elements, iron, tantalum A layer containing one or more elements selected from nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, platinum group elements Further, it may be a metal layer or an alloy layer made of one or more elements selected from the group consisting of iron, tantalum and the like. The heat-resistant layer and / or rust preventive layer is a group of nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus, arsenic, chromium, vanadium, titanium, aluminum, gold, silver, platinum group elements, iron, and tantalum. An oxide, nitride, or silicide containing one or more elements selected from the above may be included. Further, the heat-resistant layer and / or the rust preventive layer may be a layer containing a nickel-zinc alloy. Further, the heat-resistant layer and / or the rust preventive layer may be a nickel-zinc alloy layer. The nickel-zinc alloy layer may contain 50 wt% to 99 wt% nickel and 50 wt% to 1 wt% zinc, excluding inevitable impurities. The total adhesion amount of zinc and nickel in the nickel-zinc alloy layer may be 5 to 1000 mg / m ² , preferably 10 to 500 mg / m ² , preferably 20 to 100 mg / m ² . Further, the ratio of the nickel adhesion amount and the zinc adhesion amount of the layer containing the nickel-zinc alloy or the nickel-zinc alloy layer (= nickel adhesion amount / zinc adhesion amount) is 1.5 to 10. It is preferable. Further, the nickel - in adhesion amount of nickel in the zinc alloy layer is preferably from ^{0.5mg / m 2 ~500mg / m 2} , 1mg / m 2 ~50mg / m 2 - zinc alloy layer or the nickel containing More preferably. When the heat-resistant layer and / or rust prevention layer is a layer containing a nickel-zinc alloy, the interface between the copper foil and the resin substrate is eroded by the desmear liquid when the inner wall such as a through hole or via hole comes into contact with the desmear liquid. It is difficult to improve the adhesion between the copper foil and the resin substrate.

For example heat-resistant layer and / or anticorrosive layer has coating weight of 1 mg / m ² -100 mg / m ^2, preferably from 5 mg / m ² and to 50 mg / m ² of nickel or nickel alloy layer, the adhesion amount is 1 mg / m ² to 80 mg / m ^2, preferably it may be obtained by sequentially laminating a tin layer of ^{5mg / m 2 ~40mg / m 2} , wherein the nickel alloy layer of nickel - molybdenum, nickel - zinc, nickel - molybdenum - cobalt You may be comprised by any one of these. The heat-resistant layer and / or anticorrosive layer, it is ^{preferably, 10mg / m 2 ~70mg / m} 2 total deposition amount of nickel or nickel alloy and tin is 2mg / m ² ~150mg / m 2 It is more preferable. Further, the heat-resistant layer and / or the rust preventive layer is preferably [nickel or nickel adhesion amount in nickel or nickel alloy] / [tin adhesion amount] = 0.25 to 10, preferably 0.33 to 3. More preferred. When the heat-resistant layer and / or rust-preventing layer is used, the carrier-clad copper foil is processed into a printed wiring board, and the subsequent circuit peeling strength, the chemical resistance deterioration rate of the peeling strength, and the like are improved.

  In addition, you may use a well-known silane coupling agent for the silane coupling agent used for a silane coupling process, for example, using an amino-type silane coupling agent or an epoxy-type silane coupling agent, a mercapto-type silane coupling agent. Good. Silane coupling agents include vinyltrimethoxysilane, vinylphenyltrimethoxylane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, 4-glycidylbutyltrimethoxysilane, and γ-aminopropyl. Triethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-3- (4- (3-aminopropoxy) ptoxy) propyl-3-aminopropyltrimethoxysilane, imidazolesilane, triazinesilane, γ-mercaptopropyltrimethoxysilane or the like may be used.

  The silane coupling treatment layer may be formed using a silane coupling agent such as an epoxy silane, an amino silane, a methacryloxy silane, or a mercapto silane. In addition, you may use 2 or more types of such silane coupling agents in mixture. Especially, it is preferable to form using an amino-type silane coupling agent or an epoxy-type silane coupling agent.

  The amino silane coupling agent referred to here is N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3- (N-styrylmethyl-2-aminoethylamino) propyltrimethoxysilane, 3- Aminopropyltriethoxysilane, bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane, aminopropyltrimethoxysilane, N-methylaminopropyltrimethoxysilane, N-phenylaminopropyltrimethoxysilane, N- (3 -Acryloxy-2-hydroxypropyl) -3-aminopropyltriethoxysilane, 4-aminobutyltriethoxysilane, (aminoethylaminomethyl) phenethyltrimethoxysilane, N- (2-aminoethyl-3-aminopropyl) Trimethoxysilane, N (2-Aminoethyl-3-aminopropyl) tris (2-ethylhexoxy) silane, 6- (aminohexylaminopropyl) trimethoxysilane, aminophenyltrimethoxysilane, 3- (1-aminopropoxy) -3,3- Dimethyl-1-propenyltrimethoxysilane, 3-aminopropyltris (methoxyethoxyethoxy) silane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, ω-aminoundecyltrimethoxysilane, 3- (2 -N-benzylaminoethylaminopropyl) trimethoxysilane, bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane, (N, N-diethyl-3-aminopropyl) trimethoxysilane, (N, N- Dimethyl-3-aminopropyl) Limethoxysilane, N-methylaminopropyltrimethoxysilane, N-phenylaminopropyltrimethoxysilane, 3- (N-styrylmethyl-2-aminoethylamino) propyltrimethoxysilane, γ-aminopropyltriethoxysilane, N -Β (aminoethyl) γ-aminopropyltrimethoxysilane, N-3- (4- (3-aminopropoxy) ptoxy) propyl-3-aminopropyltrimethoxysilane Good.

The silane coupling treatment layer is 0.05 mg / m ^{2 to} 200 mg / m ² , preferably 0.15 mg / m ^{2 to} 20 mg / m ² , preferably 0.3 mg / m ^{2 to} 2.0 mg in terms of silicon atoms. / M ² is desirable. In the case of the above-mentioned range, the adhesiveness between the base resin and the surface-treated copper foil can be further improved.

  In addition, on the surface of an ultrathin copper layer, a roughening treatment layer, a heat-resistant layer, a rust prevention layer, a silane coupling treatment layer or a chromate treatment layer, International Publication No. WO2008 / 053878, JP2008-1111169, Patent No. 5024930 , International Publication No. WO2006 / 028207, Patent No. 4828427, International Publication No. WO2006 / 134868, Patent No. 5046927, International Publication No. WO2007 / 105635, Patent No. 5180815, JP2013-19056A. be able to.

The carrier-attached copper foil includes a resin layer on the ultrathin copper layer, the roughened layer, the heat-resistant layer, the rust-proof layer, the chromate-treated layer, or the silane coupling-treated layer. May be. The resin layer may be an insulating resin layer.
Moreover, the copper foil with a carrier may be provided with a roughening treatment layer on the carrier, and is selected from the group consisting of a roughening treatment layer, a heat-resistant layer, a rust prevention layer, a chromate treatment layer and a silane coupling treatment layer on the carrier. One or more layers may be provided. The roughening treatment layer, the heat-resistant layer, the rust prevention layer, the chromate treatment layer and the silane coupling treatment layer may be provided by using known methods, and according to the methods described in the present specification, claims and drawings. It may be provided. Providing one or more layers selected from the roughening treatment layer, heat-resistant layer, rust prevention layer, chromate treatment layer, and silane coupling treatment layer on the carrier is possible from the surface side having the roughening treatment layer, etc. When the substrate is laminated on a support such as a resin substrate, the carrier and the support are less likely to be peeled off.

  The resin layer may be an adhesive, or an insulating resin layer in a semi-cured state (B stage state) for bonding. The semi-cured state (B stage state) is a state in which there is no sticky feeling even if the surface is touched with a finger, the insulating resin layer can be stacked and stored, and a curing reaction occurs when subjected to heat treatment. Including that.

  The resin layer may contain a thermosetting resin or may be a thermoplastic resin. The resin layer may include a thermoplastic resin. The resin layer may contain a known resin, resin curing agent, compound, curing accelerator, dielectric, reaction catalyst, crosslinking agent, polymer, prepreg, skeleton material, and the like. The resin layer may be, for example, International Publication No. WO2008 / 004399, International Publication No. WO2008 / 053878, International Publication No. WO2009 / 084533, JP-A-11-5828, JP-A-11-140281, Patent 3184485, International Publication No. WO 97/02728, Japanese Patent No. 3676375, Japanese Patent Laid-Open No. 2000-43188, Japanese Patent No. 3612594, Japanese Patent Laid-Open No. 2002-179772, Japanese Patent Laid-Open No. 2002-359444, Japanese Patent Laid-Open No. 2003-302068, Japanese Patent No. 3992225, Japanese Patent Laid-Open No. 2003 No. 249739, Japanese Patent No. 4136509, Japanese Patent Application Laid-Open No. 2004-82687, Japanese Patent No. 4025177, Japanese Patent Application Laid-Open No. 2004-349654, Japanese Patent No. 4286060, Japanese Patent Application Laid-Open No. 2005-262506, Japanese Patent No. 4570070, Japanese Patent Application Laid-Open No. No. 5-53218, Japanese Patent No. 3949676, Japanese Patent No. 4178415, International Publication No. WO2004 / 005588, Japanese Patent Application Laid-Open No. 2006-257153, Japanese Patent Application Laid-Open No. 2007-326923, Japanese Patent Application Laid-Open No. 2008-11169, and Japanese Patent No. 5024930. No. WO 2006/028207, Japanese Patent No. 4828427, JP 2009-67029, International Publication No. WO 2006/134868, Japanese Patent No. 5046927, JP 2009-173017, International Publication No. WO 2007/105635, Patent No. 5180815, International Publication Number WO2008 / 114858, International Publication Number WO2009 / 008471, Japanese Patent Application Laid-Open No. 2011-14727, International Publication Number WO2009 / 001850, International Publication Number WO2009 / 145179, International Publication Number Nos. WO2011 / 068157, JP-A-2013-19056 (resins, resin curing agents, compounds, curing accelerators, dielectrics, reaction catalysts, crosslinking agents, polymers, prepregs, skeletal materials, etc.) and / or You may form using the formation method and formation apparatus of a resin layer.

  The type of the resin layer is not particularly limited. For example, epoxy resin, polyimide resin, polyfunctional cyanate ester compound, maleimide compound, polymaleimide compound, maleimide resin, aromatic maleimide resin , Polyvinyl acetal resin, urethane resin, polyethersulfone (also referred to as polyethersulfone or polyethersulfone), polyethersulfone (also referred to as polyethersulfone or polyethersulfone) resin, aromatic polyamide resin, aromatic Polyamide resin polymer, rubber resin, polyamine, aromatic polyamine, polyamideimide resin, rubber modified epoxy resin, phenoxy resin, carboxyl group-modified acrylonitrile-butadiene resin, polyphenylene oxide, bismaleimide triazine tree Fat, thermosetting polyphenylene oxide resin, cyanate ester resin, carboxylic acid anhydride, polyvalent carboxylic acid anhydride, linear polymer having crosslinkable functional group, polyphenylene ether resin, 2,2-bis (4 -Cyanatophenyl) propane, phosphorus-containing phenol compound, manganese naphthenate, 2,2-bis (4-glycidylphenyl) propane, polyphenylene ether-cyanate resin, siloxane-modified polyamideimide resin, cyanoester resin, phosphazene resin, Select from the group of rubber-modified polyamide-imide resin, isoprene, hydrogenated polybutadiene, polyvinyl butyral, phenoxy, polymer epoxy, aromatic polyamide, fluororesin, bisphenol, block copolymerized polyimide resin, and cyanoester resin It can be mentioned resins containing one or more kinds as suitable to be.

The epoxy resin has two or more epoxy groups in the molecule and can be used without any problem as long as it can be used for electric / electronic materials. The epoxy resin is preferably an epoxy resin epoxidized using a compound having two or more glycidyl groups in the molecule. Also, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type epoxy resin, novolac type epoxy resin, cresol novolac type epoxy resin, alicyclic epoxy resin, brominated (brominated) epoxy Resin, phenol novolac type epoxy resin, naphthalene type epoxy resin, brominated bisphenol A type epoxy resin, orthocresol novolac type epoxy resin, rubber modified bisphenol A type epoxy resin, glycidylamine type epoxy resin, triglycidyl isocyanurate, N, N -Glycidyl amine compounds such as diglycidyl aniline, glycidyl ester compounds such as diglycidyl tetrahydrophthalate, phosphorus-containing epoxy resins, biphenyl type epoxy resins, One or two or more types selected from the group of phenyl novolac type epoxy resin, trishydroxyphenylmethane type epoxy resin, tetraphenylethane type epoxy resin can be used, or a hydrogenated product of the epoxy resin or Halogenated substances can be used.
As the phosphorus-containing epoxy resin, a known epoxy resin containing phosphorus can be used. The phosphorus-containing epoxy resin is, for example, an epoxy resin obtained as a derivative from 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide having two or more epoxy groups in the molecule. Is preferred.

(When the resin layer contains a dielectric (dielectric filler))
The resin layer may include a dielectric (dielectric filler).
In the case where a dielectric (dielectric filler) is included in any of the above resin layers or resin compositions, it can be used for the purpose of forming the capacitor layer and increase the capacitance of the capacitor circuit. Examples of the dielectric (dielectric filler) include BaTiO ₃ , SrTiO ₃ , Pb (Zr—Ti) O ₃ (common name PZT), PbLaTiO ₃ · PbLaZrO (common name PLZT), SrBi ₂ Ta ₂ O ₉ (common name SBT), and the like. A composite oxide dielectric powder having a perovskite structure is used.

  The dielectric (dielectric filler) may be powdery. When the dielectric (dielectric filler) is in powder form, the powder characteristics of the dielectric (dielectric filler) are such that the particle size ranges from 0.01 μm to 3.0 μm, preferably 0.02 μm to 2.0 μm. It is preferable that. When the dielectric is photographed with a scanning electron microscope (SEM) and a straight line is drawn on the dielectric particle on the photograph, the length of the longest straight line across the dielectric particle is The length of the dielectric particle is defined as the diameter of the dielectric particle. Then, an average value of the diameters of the dielectric particles in the measurement visual field is defined as the dielectric particle size.

Examples of the resin and / or resin composition and / or compound contained in the resin layer include methyl ethyl ketone (MEK), cyclopentanone, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, toluene, methanol, ethanol, propylene glycol monomethyl ether , Dimethylformamide, dimethylacetamide, cyclohexanone, ethyl cellosolve, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide and the like to obtain a resin liquid (resin varnish). The surface of the copper foil with a carrier is coated on the surface of the ultrathin copper layer by, for example, a roll coater method, and then heated and dried as necessary to remove the solvent to obtain a B stage state. For example, a hot air drying furnace may be used for drying, and the drying temperature may be 100 to 250 ° C, preferably 130 to 200 ° C. The composition of the resin layer is dissolved using a solvent, and the resin solid content is 3 wt% to 70 wt%, preferably 3 wt% to 60 wt%, preferably 10 wt% to 40 wt%, more preferably 25 wt% to 40 wt%. It is good also as a resin liquid. In addition, it is most preferable at this stage from an environmental standpoint to dissolve using a mixed solvent of methyl ethyl ketone and cyclopentanone. In addition, it is preferable to use the solvent whose boiling point is the range of 50 to 200 degreeC as a solvent.
The resin layer is preferably a semi-cured resin film having a resin flow in the range of 5% to 35% when measured according to MIL-P-13949G in the MIL standard.
In this specification, the resin flow is based on MIL-P-13949G in the MIL standard. Four 10 cm square samples are sampled from a resin-treated surface-treated copper foil with a resin thickness of 55 μm. A value calculated based on Equation 1 from the result of measuring the resin outflow weight at the time when the sample was laminated (laminate) under the conditions of a press temperature of 171 ° C., a press pressure of 14 kgf / cm ² , and a press time of 10 minutes. It is.

  The surface-treated copper foil (resin-treated surface-treated copper foil) provided with the resin layer is obtained by superposing the resin layer on a substrate and then thermocompressing the whole to thermally cure the resin layer, and then the surface-treated copper foil. When is an ultra-thin copper layer of a copper foil with a carrier, the carrier is peeled off to expose the ultra-thin copper layer (of course, the surface on the intermediate layer side of the ultra-thin copper layer is exposed) The surface-treated copper foil is used in a form in which a predetermined wiring pattern is formed from the surface opposite to the surface subjected to the roughening treatment.

  When this surface-treated copper foil with resin is used, the number of prepreg materials used in the production of the multilayer printed wiring board can be reduced. In addition, the copper-clad laminate can be manufactured even if the resin layer is made thick enough to ensure interlayer insulation or no prepreg material is used. At this time, the surface smoothness can be further improved by undercoating the surface of the substrate with an insulating resin.

In addition, when the prepreg material is not used, the material cost of the prepreg material is saved and the laminating process is simplified, which is economically advantageous. Moreover, the multilayer printed wiring board manufactured by the thickness of the prepreg material is used. The thickness is reduced, and there is an advantage that an extremely thin multilayer printed wiring board having a thickness of one layer of 100 μm or less can be manufactured.
The thickness of the resin layer is preferably 0.1 to 120 μm.

When the thickness of the resin layer becomes thinner than 0.1 μm, the adhesive strength is reduced, and when the surface-treated copper foil with resin is laminated on the base material provided with the inner layer material without interposing the prepreg material, the circuit of the inner layer material It may be difficult to ensure interlayer insulation between the two. On the other hand, if the thickness of the resin layer is thicker than 120 μm, it is difficult to form a resin layer having a desired thickness in a single coating process, which may be economically disadvantageous because of extra material costs and man-hours.
In addition, when the surface-treated copper foil having a resin layer is used for manufacturing an extremely thin multilayer printed wiring board, the thickness of the resin layer is 0.1 μm to 5 μm, more preferably 0.5 μm to 5 μm, More preferably, the thickness is 1 μm to 5 μm in order to reduce the thickness of the multilayer printed wiring board.

  The copper-clad laminate of the present invention can be produced by performing an annealing treatment on a copper foil with a carrier at 160 to 220 ° C. for 5 minutes to 5 hours, and then bonding it to an insulating substrate. The carrier-treated copper foil that has been subjected to the annealing treatment has good control of the peel strength of the carrier before and after the hot press as described above. When peeling from the foil, the peel strength of the carrier is stabilized. For this reason, the manufacturing efficiency of a copper-clad laminate and also a printed wiring board using the copper-clad laminate is improved.

A printed circuit board is completed by mounting electronic components on the printed wiring board. In the present invention, the “printed wiring board” includes a printed wiring board, a printed circuit board, and a printed board on which electronic parts are mounted as described above.
In addition, an electronic device may be manufactured using the printed wiring board, an electronic device may be manufactured using a printed circuit board on which the electronic components are mounted, and a print on which the electronic components are mounted. An electronic device may be manufactured using a substrate. Below, some examples of the manufacturing process of the printed wiring board using the copper foil with a carrier which concerns on this invention are shown.

<Method for manufacturing printed wiring board>
In one embodiment of a method for producing a printed wiring board according to the present invention, a step of preparing a copper foil with a carrier and an insulating substrate according to the present invention, a step of laminating the copper foil with a carrier and an insulating substrate, and with the carrier After laminating the copper foil and the insulating substrate so that the ultrathin copper layer side faces the insulating substrate, a copper-clad laminate is formed through a step of peeling the carrier of the copper foil with carrier, and then a semi-additive method, a modified semi-conductor A step of forming a circuit by any one of an additive method, a partial additive method, and a subtractive method. It is also possible for the insulating substrate to contain an inner layer circuit.

  In the present invention, the semi-additive method refers to a method in which a thin electroless plating is performed on an insulating substrate or a copper foil seed layer, a pattern is formed, and then a conductive pattern is formed using electroplating and etching.

Therefore, in one embodiment of a method for producing a printed wiring board according to the present invention using a semi-additive method, a step of preparing a copper foil with a carrier and an insulating substrate according to the present invention,
Laminating the copper foil with carrier and an insulating substrate;
A step of peeling the carrier of the copper foil with carrier after laminating the copper foil with carrier and the insulating substrate;
Removing all of the ultrathin copper layer exposed by peeling the carrier by a method such as etching or plasma using a corrosive solution such as acid,
Providing a through hole or / and a blind via in the resin exposed by removing the ultrathin copper layer by etching;
Performing a desmear process on the region including the through hole or / and the blind via,
Providing an electroless plating layer for the region including the resin and the through hole or / and the blind via;
Providing a plating resist on the electroless plating layer;
Exposing the plating resist, and then removing the plating resist in a region where a circuit is formed;
Providing an electrolytic plating layer in a region where the circuit from which the plating resist has been removed is formed;
Removing the plating resist;
Removing the electroless plating layer in a region other than the region where the circuit is formed by flash etching or the like;
including.

In another embodiment of the method for producing a printed wiring board according to the present invention using a semi-additive method, a step of preparing the carrier-attached copper foil and the insulating substrate according to the present invention,
Laminating the copper foil with carrier and an insulating substrate;
A step of peeling the carrier of the copper foil with carrier after laminating the copper foil with carrier and the insulating substrate;
Providing a through hole or / and a blind via in the ultrathin copper layer exposed by peeling the carrier and the insulating resin substrate;
Performing a desmear process on the region including the through hole or / and the blind via,
Removing all of the ultrathin copper layer exposed by peeling the carrier by a method such as etching or plasma using a corrosive solution such as acid,
Providing an electroless plating layer for the resin and the region including the through hole or / and the blind via exposed by removing the ultrathin copper layer by etching or the like;
Providing a plating resist on the electroless plating layer;
Exposing the plating resist, and then removing the plating resist in a region where a circuit is formed;
Providing an electrolytic plating layer in a region where the circuit from which the plating resist has been removed is formed;
Removing the plating resist;
Removing the electroless plating layer in a region other than the region where the circuit is formed by flash etching or the like;
including.

In another embodiment of the method for producing a printed wiring board according to the present invention using a semi-additive method, a step of preparing the carrier-attached copper foil and the insulating substrate according to the present invention,
Laminating the copper foil with carrier and an insulating substrate;
A step of peeling the carrier of the copper foil with carrier after laminating the copper foil with carrier and the insulating substrate;
Providing a through hole or / and a blind via in the ultrathin copper layer exposed by peeling the carrier and the insulating resin substrate;
Removing all of the ultrathin copper layer exposed by peeling the carrier by a method such as etching or plasma using a corrosive solution such as acid,
Performing a desmear process on the region including the through hole or / and the blind via,
Providing an electroless plating layer for the resin and the region including the through hole or / and the blind via exposed by removing the ultrathin copper layer by etching or the like;
Providing a plating resist on the electroless plating layer;
Exposing the plating resist, and then removing the plating resist in a region where a circuit is formed;
Providing an electrolytic plating layer in a region where the circuit from which the plating resist has been removed is formed;
Removing the plating resist;
Removing the electroless plating layer in a region other than the region where the circuit is formed by flash etching or the like;
including.

In another embodiment of the method for producing a printed wiring board according to the present invention using a semi-additive method, a step of preparing the carrier-attached copper foil and the insulating substrate according to the present invention,
Laminating the copper foil with carrier and an insulating substrate;
A step of peeling the carrier of the copper foil with carrier after laminating the copper foil with carrier and the insulating substrate;
Removing all of the ultrathin copper layer exposed by peeling the carrier by a method such as etching or plasma using a corrosive solution such as acid,
Providing an electroless plating layer on the surface of the resin exposed by removing the ultrathin copper layer by etching;
Providing a plating resist on the electroless plating layer;
Exposing the plating resist, and then removing the plating resist in a region where a circuit is formed;
Providing an electrolytic plating layer in a region where the circuit from which the plating resist has been removed is formed;
Removing the plating resist;
Removing the electroless plating layer and the ultrathin copper layer in a region other than the region where the circuit is formed by flash etching or the like;
including.

  In the present invention, the modified semi-additive method is a method in which a metal foil is laminated on an insulating layer, a non-circuit forming portion is protected by a plating resist, and the copper is thickened in the circuit forming portion by electrolytic plating, and then the resist is removed. Then, a method of forming a circuit on the insulating layer by removing the metal foil other than the circuit forming portion by (flash) etching is indicated.

Therefore, in one embodiment of the method for producing a printed wiring board according to the present invention using the modified semi-additive method, the step of preparing the copper foil with carrier and the insulating substrate according to the present invention,
Laminating the copper foil with carrier and an insulating substrate;
A step of peeling the carrier of the copper foil with carrier after laminating the copper foil with carrier and the insulating substrate;
Providing a through hole or / and a blind via on the insulating substrate and the ultrathin copper layer exposed by peeling the carrier;
Performing a desmear process on the region including the through hole or / and the blind via,
Providing an electroless plating layer for the region including the through hole or / and the blind via;
Providing a plating resist on the surface of the ultrathin copper layer exposed by peeling the carrier,
Forming a circuit by electrolytic plating after providing the plating resist;
Removing the plating resist;
Removing the ultra-thin copper layer exposed by removing the plating resist by flash etching;
including.

In another embodiment of the method for producing a printed wiring board according to the present invention using the modified semi-additive method, the step of preparing the carrier-attached copper foil and the insulating substrate according to the present invention,
Laminating the copper foil with carrier and an insulating substrate;
A step of peeling the carrier of the copper foil with carrier after laminating the copper foil with carrier and the insulating substrate;
Providing a plating resist on the exposed ultrathin copper layer by peeling off the carrier;
Exposing the plating resist, and then removing the plating resist in a region where a circuit is formed;
Providing an electrolytic plating layer in a region where the circuit from which the plating resist has been removed is formed;
Removing the plating resist;
Removing an ultrathin copper layer in a region other than the region where the circuit is formed by flash etching or the like;
including.

  In the present invention, the partial additive method means that a catalyst circuit is formed on a substrate provided with a conductor layer, and if necessary, a substrate provided with holes for through holes or via holes, and etched to form a conductor circuit. Then, after providing a solder resist or a plating resist as necessary, on the conductor circuit, by performing a thickness by electroless plating treatment (further electrolytic plating treatment if necessary) on a through hole or via hole, It refers to a method of manufacturing a printed wiring board.

Therefore, in one embodiment of the method for producing a printed wiring board according to the present invention using a partly additive method, a step of preparing the copper foil with carrier and the insulating substrate according to the present invention,
Laminating the copper foil with carrier and an insulating substrate;
A step of peeling the carrier of the copper foil with carrier after laminating the copper foil with carrier and the insulating substrate;
Providing a through hole or / and a blind via on the insulating substrate and the ultrathin copper layer exposed by peeling the carrier;
Performing a desmear process on the region including the through hole or / and the blind via,
Applying catalyst nuclei to the region containing the through-holes and / or blind vias;
Providing an etching resist on the surface of the ultrathin copper layer exposed by peeling the carrier,
Exposing the etching resist to form a circuit pattern;
Removing the ultrathin copper layer and the catalyst nucleus by a method such as etching or plasma using a corrosive solution such as an acid to form a circuit;
Removing the etching resist;
A step of providing a solder resist or a plating resist on the surface of the insulating substrate exposed by removing the ultrathin copper layer and the catalyst core by a method such as etching or plasma using a corrosive solution such as an acid;
Providing an electroless plating layer in a region where the solder resist or plating resist is not provided,
including.

  In the present invention, the subtractive method refers to a method of forming a conductor pattern by selectively removing unnecessary portions of a copper foil on a copper clad laminate by etching or the like.

Therefore, in one embodiment of the method for producing a printed wiring board according to the present invention using a subtractive method, a step of preparing the carrier-attached copper foil and the insulating substrate according to the present invention,
Laminating the copper foil with carrier and an insulating substrate;
A step of peeling the carrier of the copper foil with carrier after laminating the copper foil with carrier and the insulating substrate;
Providing a through hole or / and a blind via on the insulating substrate and the ultrathin copper layer exposed by peeling the carrier;
Performing a desmear process on the region including the through hole or / and the blind via,
Providing an electroless plating layer for the region including the through hole or / and the blind via;
Providing an electroplating layer on the surface of the electroless plating layer;
A step of providing an etching resist on the surface of the electrolytic plating layer or / and the ultrathin copper layer;
Exposing the etching resist to form a circuit pattern;
Removing the ultrathin copper layer and the electroless plating layer and the electrolytic plating layer by a method such as etching or plasma using a corrosive solution such as an acid to form a circuit;
Removing the etching resist;
including.

In another embodiment of the method for producing a printed wiring board according to the present invention using a subtractive method, a step of preparing the carrier-attached copper foil and the insulating substrate according to the present invention,
Laminating the copper foil with carrier and an insulating substrate;
A step of peeling the carrier of the copper foil with carrier after laminating the copper foil with carrier and the insulating substrate;
Providing a through hole or / and a blind via on the insulating substrate and the ultrathin copper layer exposed by peeling the carrier;
Performing a desmear process on the region including the through hole or / and the blind via,
Providing an electroless plating layer for the region including the through hole or / and the blind via;
Forming a mask on the surface of the electroless plating layer;
Providing an electroplating layer on the surface of the electroless plating layer on which no mask is formed;
A step of providing an etching resist on the surface of the electrolytic plating layer or / and the ultrathin copper layer;
Exposing the etching resist to form a circuit pattern;
Removing the ultra-thin copper layer and the electroless plating layer by a method such as etching or plasma using a corrosive solution such as an acid to form a circuit;
Removing the etching resist;
including.

  The process of providing a through hole or / and a blind via and the subsequent desmear process may not be performed.

Here, the specific example of the manufacturing method of the printed wiring board using the copper foil with a carrier of this invention is demonstrated in detail using drawing. Here, the carrier-attached copper foil having an ultrathin copper layer on which a roughened layer is formed will be described as an example. However, the present invention is not limited thereto, and the carrier has an ultrathin copper layer on which a roughened layer is not formed. The following method for producing a printed wiring board can be similarly performed using an attached copper foil.
First, as shown to FIG. 1-A, the copper foil with a carrier (1st layer) which has the ultra-thin copper layer in which the roughening process layer was formed on the surface is prepared.
Next, as shown in FIG. 1-B, a resist is applied onto the roughened layer of the ultrathin copper layer, exposed and developed, and etched into a predetermined shape.
Next, as shown in FIG. 1-C, after the plating for the circuit is formed, the resist is removed to form a circuit plating having a predetermined shape.
Next, as shown in FIG. 2-D, an embedding resin is provided on the ultrathin copper layer so as to cover the circuit plating (so that the circuit plating is buried), and then the resin layer is laminated, followed by another carrier. A copper foil (second layer) is bonded from the ultrathin copper layer side.
Next, as shown to FIG. 2-E, a carrier is peeled from the copper foil with a carrier of the 2nd layer.
Next, as shown in FIG. 2-F, laser drilling is performed at a predetermined position of the resin layer to expose the circuit plating and form a blind via.
Next, as shown in FIG. 3G, copper is embedded in the blind via to form a via fill.
Next, as shown in FIG. 3H, circuit plating is formed on the via fill as shown in FIGS. 1-B and 1-C.
Next, as shown to FIG. 3-I, a carrier is peeled from the copper foil with a carrier of the 1st layer.
Next, as shown in FIG. 4J, the ultrathin copper layers on both surfaces are removed by flash etching, and the surface of the circuit plating in the resin layer is exposed.
Next, as shown in FIG. 4K, bumps are formed on the circuit plating in the resin layer, and copper pillars are formed on the solder. Thus, the printed wiring board using the copper foil with a carrier of this invention is produced.

  As the another copper foil with a carrier (second layer), the copper foil with a carrier of the present invention may be used, a conventional copper foil with a carrier may be used, and a normal copper foil may be further used. Further, one or more circuits may be formed on the second layer circuit shown in FIG. 3H, and these circuits may be formed by a semi-additive method, a subtractive method, a partial additive method, or a modified semi-conductor method. You may carry out by any method of an additive method.

  Moreover, the copper foil with a carrier used for the said 1st layer may have a board | substrate on the carrier side surface of the said copper foil with a carrier. By having the said board | substrate, since the copper foil with a carrier used for the 1st layer is supported and it becomes difficult to wrinkle, there exists an advantage that productivity improves. As the substrate, any substrate can be used as long as it has an effect of supporting the carrier-attached copper foil used in the first layer. For example, the carrier, prepreg, resin layer or known carrier, prepreg, resin layer, metal plate, metal foil, inorganic compound plate, inorganic compound foil, organic compound plate, organic compound A foil can be used.

  Although there is no restriction | limiting in particular about the timing which forms a board | substrate in the carrier side surface, It is necessary to form before peeling a carrier. In particular, it is preferably formed before the step of forming a resin layer on the ultrathin copper layer side surface of the copper foil with carrier, and the step of forming a circuit on the ultrathin copper layer side surface of the copper foil with carrier More preferably, it is formed before.

  A known resin or prepreg can be used as the embedding resin (resin). For example, a prepreg that is a glass cloth impregnated with BT (bismaleimide triazine) resin or BT resin, an ABF film or ABF manufactured by Ajinomoto Fine Techno Co., Ltd. can be used. The embedding resin may include a thermosetting resin or a thermoplastic resin. The embedding resin may include a thermoplastic resin. The type of the embedded resin is not particularly limited. For example, epoxy resin, polyimide resin, polyfunctional cyanate compound, maleimide compound, polyvinyl acetal resin, urethane resin, block copolymer polyimide resin, block copolymer Resin including polyimide resin, paper base phenolic resin, paper base epoxy resin, synthetic fiber cloth base epoxy resin, glass cloth / paper composite base epoxy resin, glass cloth / glass non-woven composite base epoxy resin and glass A cloth base epoxy resin, a polyester film, a polyimide film, a liquid crystal polymer film, a fluororesin film, etc. can be mentioned as a suitable thing.

Moreover, the manufacturing method of the printed wiring board of this invention is the process of laminating | stacking the said ultra-thin copper layer side surface or the said carrier side surface, and the resin substrate of the copper foil with a carrier of this invention, The surface treatment laminated | stacked with the said resin substrate On the surface of the layer-side surface or the copper foil with carrier on the side opposite to the carrier-side surface, a step of providing two layers of a resin layer and a circuit at least once, and two layers of the resin layer and the circuit were formed A printed wiring board manufacturing method (coreless method) including a step of peeling the carrier or the ultrathin copper layer from the copper foil with carrier may be used later. As a specific example of the coreless construction method, first, the surface treatment layer side surface or carrier side surface of the copper foil with carrier of the present invention and a resin substrate are laminated. Thereafter, a resin layer is formed on the surface of the surface-treated layer side laminated with the resin substrate or the surface of the carrier-attached copper foil opposite to the carrier side surface. Another copper foil with a carrier may be laminated from the carrier side or the surface treatment layer side to the resin layer formed on the carrier side surface or the surface treatment layer side surface. In this case, the carrier is in the order of carrier / intermediate layer / ultra thin copper layer / surface treatment layer or surface treatment layer / ultra thin copper layer / intermediate layer / carrier on both surfaces of the resin substrate with the resin substrate as the center. It has a structure in which a copper foil is laminated. Another resin layer may be provided on the surface treatment layer on both ends or the exposed surface of the carrier, and a copper layer or a metal layer may be further provided, and then the copper layer or the metal layer may be processed to form a circuit. . Further, another resin layer may be provided on the circuit so as to embed the circuit. Further, such a circuit and a resin layer may be formed one or more times (build-up method). And about the laminated body formed in this way (henceforth the laminated body B), a coreless board | substrate is produced by peeling the ultra-thin copper layer or carrier of each copper foil with a carrier from a carrier or an ultra-thin copper layer. be able to. In addition, for the preparation of the coreless substrate described above, two copper foils with a carrier were used, and a surface treatment layer / ultra thin copper layer / intermediate layer / carrier / carrier / intermediate layer / ultra thin copper layer / surface treatment layer described later. Laminates having the structure of: carrier / intermediate layer / ultra-thin copper layer surface treatment layer / surface treatment layer / ultra-thin copper layer / intermediate layer / laminated bodies and carrier / intermediate layer / ultra-thin copper A laminate having a structure of layer / surface treatment layer / carrier / intermediate layer / ultra-thin copper layer / surface treatment layer can be produced, and the laminate can be used mainly. Two layers of the resin layer and the circuit are provided at least once on the surface of the ultra-thin copper layer or carrier on both sides of these laminates (hereinafter also referred to as the laminate A), and the two layers of the resin layer and the circuit are provided at least once. Later, the coreless substrate can be manufactured by peeling off the ultrathin copper layer or carrier of each copper foil with carrier from the carrier or the ultrathin copper layer. The above-mentioned laminate includes the surface of the surface treatment layer, between the surface treatment layer and the ultrathin copper layer, the surface of the carrier, between the carrier and the carrier, between the surface treatment layer and the surface treatment layer, and the ultrathin copper layer. There may be another layer between the carrier and the carrier. In this specification, “surface of the surface treatment layer”, “surface of the surface treatment layer”, “surface of the carrier”, “surface of the carrier”, “carrier surface”, “surface of the laminate”, “surface of the laminate” In the case where the surface treatment layer, carrier, and laminate have other layers on the surface treatment layer surface, carrier surface, and laminate surface, the concept includes the surface (outermost surface) of the other layer. Moreover, it is preferable that a laminated body has the structure of surface treatment layer / ultra thin copper layer / intermediate layer / carrier / carrier / intermediate layer / ultra thin copper layer / surface treatment layer. This is because, when a coreless substrate is manufactured using the laminate, an ultrathin copper layer is disposed on the coreless substrate side, so that a circuit can be easily formed on the coreless substrate using the modified semi-additive method. In addition, since the thickness of the ultrathin copper layer is thin, it is easy to remove the ultrathin copper layer, and it becomes easier to form a circuit on the coreless substrate using the semi-additive method after the ultrathin copper layer is removed. .
In this specification, “laminate” not specifically described as “laminate A” or “laminate B” indicates a laminate including at least laminate A and laminate B.

  In the above-described coreless substrate manufacturing method, by covering part or all of the end face of the copper foil with carrier or the laminate (laminate A) with a resin, when producing a printed wiring board by the build-up method, It is possible to prevent the infiltration of the chemical solution between one copper foil with a carrier and another copper foil with a carrier constituting the intermediate layer or laminate, and separation of the ultrathin copper layer and the carrier due to the infiltration of the chemical solution or the carrier Corrosion of the attached copper foil can be prevented, and the yield can be improved. As the “resin that covers part or all of the end face of the copper foil with carrier” or “resin that covers part or all of the end face of the laminate” used herein, a resin that can be used for the resin layer may be used. it can. Further, in the above-described coreless substrate manufacturing method, the carrier-attached copper foil or laminate when viewed in plan, the carrier-attached copper foil or laminate portion (a laminate portion of the carrier and the ultrathin copper layer, or one At least a part of the outer periphery of the laminated copper foil with carrier and another copper foil with carrier may be covered with resin or prepreg. Moreover, the laminated body (laminated body A) formed with the manufacturing method of the above-mentioned coreless board | substrate may be comprised by making a pair of copper foil with a carrier contact each other so that isolation | separation is possible. Further, when viewed in plan in the copper foil with carrier, the copper foil with carrier or the laminated portion of the laminated body (the laminated portion of the carrier and the ultrathin copper layer, or one copper foil with carrier and another copper with carrier) It may be formed by being covered with a resin or a prepreg over the entire outer periphery of the laminated portion with the foil. By adopting such a configuration, when the copper foil with a carrier or a laminate is viewed in plan, the laminated portion of the copper foil with a carrier or the laminate is covered with a resin or prepreg, and other members are in the lateral direction of this portion. That is, it becomes possible to prevent the stacking direction from being hit from the side, and as a result, peeling of the carrier during handling and the ultrathin copper layer or the copper foil with carrier can be reduced. Moreover, by covering the outer periphery of the copper foil with a carrier or the laminated part with a resin or prepreg so as not to be exposed, it is possible to prevent the chemical solution from entering the interface of the laminated part in the chemical treatment process as described above. , Corrosion and erosion of the copper foil with carrier can be prevented. When separating a single copper foil with a carrier from a pair of copper foils with a carrier, or when separating a carrier of a copper foil with a carrier and a copper foil (ultra-thin copper layer), a resin or prepreg is used. Cutting a covered copper foil with a carrier or a laminated part of a laminated body (a laminated part of a carrier and an ultrathin copper layer or a laminated part of one copper foil with a carrier and another copper foil with a carrier), etc. Need to be removed.

  The copper foil with a carrier of the present invention may be laminated from the carrier side or surface treatment layer side to the carrier side or the surface treatment layer side of another copper foil with carrier of the present invention to constitute a laminate. Also, the carrier-side surface or the surface treatment layer side surface of the one carrier-attached copper foil and the carrier-side surface or the surface treatment layer side surface of the another carrier-attached copper foil are bonded as necessary. A laminate obtained by directly laminating through an agent may be used. The carrier or surface treatment layer of the one copper foil with carrier and the carrier or surface treatment layer of the other copper foil with carrier may be bonded. Further, part or all of the end face of the laminate may be covered with resin.

Lamination of carriers can be performed by, for example, the following method, in addition to simply overlapping.
(A) Metallurgical joining method: fusion welding (arc welding, TIG (tungsten inert gas) welding, MIG (metal inert gas) welding, resistance welding, seam welding, spot welding), pressure welding (ultrasonic welding, Friction stir welding), brazing;
(B) Mechanical joining method: caulking, joining with rivets (joining with self-piercing rivets, joining with rivets), stitcher;
(C) Physical joining method: adhesive, (double-sided) adhesive tape

  By joining a part or all of one carrier and a part or all of the other carrier using the joining method described above, one carrier and the other carrier are stacked, and the carriers are brought into contact with each other in a separable manner. Thus, it is possible to manufacture a laminated body constituted. When one carrier and the other carrier are weakly joined and one carrier and the other carrier are laminated, one carrier is not removed even if the joint between the one carrier and the other carrier is not removed. And the other carrier can be separated. In addition, when one carrier and the other carrier are strongly bonded, the portion where one carrier and the other carrier are bonded is removed by cutting, chemical polishing (etching, etc.), mechanical polishing, or the like. Thus, one carrier and the other carrier can be separated.

  Also, a step of providing at least one layer of the resin layer and the circuit on the laminate thus configured, and after forming the two layers of the resin layer and the circuit at least once, the carrier of the laminate is provided with a carrier. A printed wiring board can be produced by carrying out a process of peeling the ultrathin copper layer or carrier from the copper foil. Note that two layers of a resin layer and a circuit may be provided on one or both surfaces of the laminate.

  The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples.

1. Preparation of copper foil with carrier [Carrier]
An electrolytic copper foil was produced under the following conditions and used as a carrier.
(Examples and Comparative Example Carriers)
<Electrolytic solution composition>
Copper: 80-110 g / L
Sulfuric acid: 70-110 g / L
Chlorine: 10-100 ppm by mass
Nika: 0.01-0.1 mass ppm
<Production conditions>
Current density: 50 to 200 A / dm ²
Electrolyte temperature: 40-70 ° C
Electrolyte linear velocity: 3-5 m / sec
Electrolysis time: 0.5 to 10 minutes

[Middle layer]
As shown in Table 1 for each example and comparative example, the following intermediate layer was provided.
For example, “Ni / chromate” in Table 1 means that the following chromate treatment layer is provided after the following Ni layer is provided on the surface of the carrier.
-"Ni": Ni layer A predetermined amount of Ni layer was formed on the shiny surface of the copper foil by electroplating on a roll-to-roll-type continuous plating line under the following conditions.
<Electrolytic solution composition>
Nickel sulfate: 270-280 g / L
Nickel chloride: 35 to 45 g / L
Nickel acetate: 10-20g / L
Trisodium citrate: 15-25 g / L
Brightener: Saccharin, butynediol, etc. Sodium dodecyl sulfate: 55-75 mass ppm
pH: 4-6
Bath temperature: 55-65 ° C
Current density: 7 to 11 A / dm ²

・ "Chromate": chromate treatment layer, electrolytic chromate treatment Liquid composition: potassium dichromate 1-10g / L, Zn0-10g / L
pH: 7-10
Liquid temperature: 40-60 degreeC
Current density: 0.1-2.6 A / dm ²
Coulomb amount: 0.5-30 As / dm ²
・ "Ni-Mo": Ni-Mo layer (nickel molybdenum alloy plating)
(Liquid composition) Ni sulfate hexahydrate: 50 g / dm ³ , sodium molybdate dihydrate: 60 g / dm ³ , sodium citrate: 90 g / dm ³
(Liquid temperature) 30 ° C
(Current density) 1 to 4 A / dm ²
(Energization time) 3 to 25 seconds ・ "Organic substance": Organic substance layer (Organic substance layer forming treatment)
An organic layer was formed by spraying an aqueous solution containing carboxybenzotriazole (CBTA) having a concentration of 1 to 30 g / L and having a liquid temperature of 40 ° C. and a pH of 5 for 20 to 120 seconds.
"Co-Mo": Co-Mo layer (cobalt molybdenum alloy plating)
(Liquid composition) Co sulfate 50 g / dm ³ , sodium molybdate dihydrate: 60 g / dm ³ , sodium citrate: 90 g / dm ³
(Liquid temperature) 30 ° C
(Current density) 1 to 4 A / dm ²
(Energization time) 3 to 25 sec. “Cr”: Chromium layer (Liquid composition) CrO ₃ : 200 to 400 g / L, H ₂ SO ₄ : 1.5 to ₄ g / L
(PH) 1-4
(Liquid temperature) 45-60 ° C
(Current density) 10-40 A / dm ²

(Ultra-thin copper layer)
Subsequently, on a roll-to-roll type continuous plating line, an ultrathin copper layer having a thickness of 1 to 10 μm was formed on the intermediate layer by electroplating under the following conditions to produce a copper foil with a carrier.
Copper concentration: 30-120 g / L
H ₂ SO ₄ concentration: 20 to 120 g / L
Electrolyte temperature: 20-80 ° C
Current density: 10 to 100 A / dm ²

[Surface treatment layer]
For Example 2 and Comparative Example 2, the surface of the ultrathin copper layer was subjected to the following roughening treatment, rust prevention treatment, chromate treatment, and silane coupling treatment in this order.
・ Roughening Cu: 10 to 20 g / L
Co: 1-10 g / L
Ni: 1 to 10 g / L
pH: 1-4
Liquid temperature: 40-50 degreeC
Current density Dk: 20 to 30 A / dm ²
Time: 1-5 seconds Cu adhesion amount: 15-40 mg / dm ²
Co adhesion amount: 100 to 3000 μg / dm ²
Ni adhesion amount: 100 to 1000 μg / dm ²
・ Rust prevention treatment Zn: over 0 to 20 g / L
Ni: more than 0 to 5 g / L
pH: 2.5-4.5
Liquid temperature: 30-50 degreeC
Current density Dk: more than 0 to 1.7 A / dm ²
Time: 1 second Zn deposition amount: 5-250 μg / dm ²
Ni adhesion amount: 5 to 300 μg / dm ²
・ Chromate treatment K ₂ Cr ₂ O ₇
(Na ₂ Cr ₂ O ₇ or CrO ₃ ): 2 to 10 g / L
NaOH or KOH: 10-50 g / L
ZnO or ZnSO ₄ .7H ₂ O: 0.05 to 10 g / L
pH: 7-13
Bath temperature: 20-80 ° C
Current density 0.05-5A / dm ²
Time: 5 to 30 seconds Cr adhesion amount: 10 to 150 μg / dm ²
・ Silane coupling treatment Vinyltriethoxysilane aqueous solution (vinyltriethoxysilane concentration: 0.1 to 1.4 wt%)
pH: 4-5
Bath temperature: 25-60 ° C
Immersion time: 5 to 30 seconds

For Examples 3, 6, and 11 and Comparative Example 3, the following roughening treatment 1, roughening treatment 2, antirust treatment, chromate treatment, and silane coupling treatment were applied to the surface of the ultrathin copper layer. I went in order.
・ Roughening 1
(Liquid composition 1)
Cu: 10-30 g / L
H ₂ SO _4: 10~150g / L
W: 0 to 50 mg / L
Sodium dodecyl sulfate: 0 to 50 mg / L
As: 0 to 200 mg / L
(Electroplating condition 1)
Temperature: 30-70 ° C
Current density: 25 to 110 A / dm ²
Roughening coulomb amount: 50 to 500 As / dm ²
Plating time: 0.5 to 20 seconds, roughening treatment 2
(Liquid composition 2)
Cu: 20-80 g / L
H ₂ SO ₄ : 50 to 200 g / L
(Electroplating condition 2)
Temperature: 30-70 ° C
Current density: 5 to 50 A / dm ²
Roughening coulomb amount: 50 to 300 As / dm ²
Plating time: 1 to 60 seconds, rust prevention treatment (liquid composition)
NaOH: 40-200 g / L
NaCN: 70 to 250 g / L
CuCN: 50-200 g / L
Zn (CN) ₂ : _{2 to} 100 g / L
As ₂ O ₃ : 0.01 to 1 g / L
(Liquid temperature)
40-90 ° C
(Current condition)
Current density: 1 to 50 A / dm ²
Plating time: 1 to 20 seconds, chromate treatment K ₂ Cr ₂ O ₇ (Na ₂ Cr ₂ O ₇ or CrO ₃ ): 2 to 10 g / L
NaOH or KOH: 10-50 g / L
ZnOH or ZnSO ₄ .7H ₂ O: 0.05 to 10 g / L
pH: 7-13
Bath temperature: 20-80 ° C
Current density: 0.05 to 5 A / dm ²
Time: 5 to 30 seconds. Silane coupling treatment After applying 0.1 vol% to 0.3 vol% of 3-glycidoxypropyltrimethoxysilane aqueous solution, 0.1 to 10 in air at 100 to 200 ° C. Dry and heat for seconds.

For Example 4 and Comparative Example 4, the following roughening treatment 1, roughening treatment 2, rust prevention treatment, chromate treatment, and silane coupling treatment were performed in this order on the surface of the ultrathin copper layer.
・ Roughening 1
Liquid composition: Copper 10-20 g / L, sulfuric acid 50-100 g / L
Liquid temperature: 25-50 degreeC
Current density: 1 to 58 A / dm ²
Coulomb amount: 4 to 81 As / dm ²
・ Roughening 2
Liquid composition: Copper 10-20 g / L, nickel 5-15 g / L, cobalt 5-15 g / L
pH: 2-3
Liquid temperature: 30-50 degreeC
Current density: 24 to 50 A / dm ²
Coulomb amount: 34 to 48 As / dm ²
・ Rust prevention treatment Liquid composition: Nickel 5-20g / L, Cobalt 1-8g / L
pH: 2-3
Liquid temperature: 40-60 degreeC
Current density: 5 to 20 A / dm ²
Coulomb amount: 10-20 As / dm ²
-Chromate treatment Liquid composition: Potassium dichromate 1-10 g / L, Zinc 0-5 g / L
pH: 3-4
Liquid temperature: 50-60 degreeC
Current density: 0 to ^{2 A} / dm ² (Can also be electroless because of immersion chromate treatment)
Coulomb amount: 0 to ^{2 As} / dm ² (can also be electroless because of immersion chromate treatment)
Silane coupling treatment Application of diaminosilane aqueous solution (diaminosilane concentration: 0.1 to 0.5 wt%)

  Next, each sample was annealed under the conditions of “heating temperature” and “heating time” shown in Table 1 to prepare a copper foil with a carrier.

2. Evaluation of copper foil with carrier <Evaluation of thickness of ultrathin copper layer>
The thickness of the ultra-thin copper layer of the produced copper foil with a carrier was observed using FIB-SIM (magnification: 10,000 to 30,000 times). A cross section parallel to the plate thickness direction of the ultrathin copper layer was observed, the thickness of the ultrathin copper layer at five locations was measured at intervals of 30 μm on the cross section, and the average value was taken as the thickness of the ultrathin copper layer.

<Evaluation of peel strength>
(1) Peeling strength before hot pressing: About the produced copper foil with a carrier, the carrier side was pulled with the load cell, and it measured based on the 90 degree peeling method (JIS C6471 8.1).
(2) Peel strength after hot pressing: The ultrathin copper layer side of the produced copper foil with carrier is bonded to an insulating substrate, and heated and pressed in air at 20 kgf / cm ² and 220 ° C. for 2 hours. Then, the carrier side was pulled with a load cell, and measurement was performed in accordance with a 90 ° peeling method (JIS C 6471 8.1).
Using the peel strengths obtained in (1) and (2) above, the peel strength change rate A: (peel strength after hot pressing / peel strength before hot press) × 100% was calculated.

<Metal adhesion amount of intermediate layer>
The amount of nickel adhered was measured by ICP emission analysis using an ICP emission spectrophotometer (model: SPS3100) manufactured by SII after dissolving the sample with nitric acid having a concentration of 20% by mass. Dissolved in hydrochloric acid with a concentration of 7% by mass at 100 ° C., and measured by quantitative analysis by atomic absorption method using an atomic absorption spectrophotometer (model: AA240FS) manufactured by VARIAN. The sample was dissolved in a mixed solution of nitric acid and hydrochloric acid (nitric acid concentration: 20% by mass, hydrochloric acid concentration: 12% by mass), and atomic absorption was performed using an atomic absorption spectrophotometer (model: AA240FS) manufactured by VARIAN. Measured by quantitative analysis by the method. The nickel, zinc, chromium, molybdenum and cobalt adhesion amounts were measured as follows. First, after peeling the ultra-thin copper layer from the copper foil with carrier, only the vicinity of the surface on the intermediate layer side of the ultra-thin copper layer is dissolved (only the thickness of 0.5 μm is dissolved from the surface). The amount of adhesion on the surface on the intermediate layer side is measured. Further, after peeling off the ultrathin copper layer, only the vicinity of the surface on the intermediate layer side of the carrier is dissolved (only the thickness of 0.5 μm from the surface is dissolved), and the amount of adhesion on the surface of the carrier on the intermediate layer side is measured. And the value which totaled the adhesion amount of the surface by the side of the intermediate | middle layer of an ultra-thin copper layer and the adhesion amount of the surface by the side of the intermediate | middle layer of a carrier was made into the metal adhesion amount of an intermediate | middle layer. In addition, when the unevenness of the ultrathin copper layer is large and the thickness of the ultrathin copper layer is 1.5 μm or less, the thickness of 0.5 μm was dissolved from the surface on the intermediate layer side of the ultrathin copper layer. In some cases, the roughening component on the surface of the ultrathin copper layer may also dissolve. Therefore, in such a case, 30% of the thickness of the ultrathin copper layer on the intermediate layer side is dissolved.
When the sample is difficult to dissolve in nitric acid having a concentration of 20% by mass or hydrochloric acid having a concentration of 7% by mass, a mixed solution of nitric acid and hydrochloric acid (nitric acid concentration: 20% by mass, hydrochloric acid concentration: 12% by mass) After dissolving the sample, the amount of nickel, zinc and chromium deposited can be measured by the above-described method.
The “metal adhesion amount” means the metal adhesion amount (mass) per sample unit area (1 dm ² ).

<Thickness of organic material in the intermediate layer>
After peeling the ultrathin copper layer of the carrier-attached copper foil from the carrier, XPS measurement was performed on the surface of the exposed ultrathin copper layer on the intermediate layer side and the surface of the exposed carrier on the intermediate layer side to create a depth profile. The depth at which the carbon concentration first becomes 3 at% or less from the surface on the intermediate layer side of the ultrathin copper layer is defined as A (nm), and the carbon concentration is initially 3 at% or less from the surface on the intermediate layer side of the carrier. The resulting depth was defined as B (nm), and the sum of A and B was defined as the thickness (nm) of the organic substance in the intermediate layer. Note that the measurement interval of the atomic concentration of the metal in the depth direction (x: unit nm) is preferably 0.18 to 0.30 nm (in terms of SiO ₂ ). In this example, the atomic concentration of the metal in the depth direction was measured at 0.28 nm (SiO ₂ equivalent) intervals (measured every 0.1 minutes by sputtering time).
In addition, the depth profile of the carbon concentration by the XPS measurement is as follows. A total of three locations, one in each region within 50 mm and one in a 50 mm × 50 mm region at the center, that is, the surface on the intermediate layer side of the exposed ultrathin copper layer and the intermediate layer side of the exposed carrier A total of six locations were created on the surface. FIG. 5 shows three measurement points on the surface on the intermediate layer side of the exposed ultrathin copper layer and three points on the surface on the intermediate layer side of the exposed carrier. Subsequently, from the depth profile created for each of the three regions on the exposed intermediate layer side surface of the exposed ultrathin copper layer and the exposed intermediate layer side of the carrier, on the intermediate layer side of the above described ultrathin copper layer, respectively. The depth A (nm) at which the carbon concentration first became 3 at% or less from the surface, and the depth B (nm) at which the carbon concentration first became 3 at% or less from the surface on the intermediate layer side of the carrier were calculated. The sum of the arithmetic average value of A (nm) and the arithmetic average value of B (nm) was defined as the thickness (nm) of the organic substance in the intermediate layer.
When the sample size is small, the above-mentioned region within 50 mm from both ends and the 50 mm × 50 mm region at the center may overlap.
XPS operating conditions are shown below.
・ Device: XPS measuring device (ULVAC-PHI, Model 5600MC)
・ Achieving vacuum: 3.8 × 10 ⁻⁷ Pa
X-ray: Monochromatic AlKα or non-monochromatic MgKα, X-ray output 300 W, detection area 800 μmφ, angle between sample and detector 45 °
Ion beam: ion species Ar ⁺ , acceleration voltage 3 kV, sweep area 3 mm × 3 mm, sputtering rate 2.8 nm / min (in terms of SiO ₂ )
XPS means X-ray photoelectron spectroscopy. In the present invention, it is assumed that an XPS measuring device (model 5600MC or an equivalent measuring device manufactured and sold by ULVAC-PHI) is used by ULVAC-PHI. If such a measuring device cannot be obtained, Other XPS measurements can be performed by setting the measurement interval of each element concentration in the depth direction to 0.10 to 0.30 nm (converted to SiO ₂ ) and the sputtering rate to 1.0 to 3.0 nm / min (converted to SiO ₂ ). An apparatus may be used.
Test conditions and test results are shown in Tables 1 and 2.

(Evaluation results)
In each of Examples 1 to 52, the carrier peel strength after hot pressing the carrier-attached copper foil under the conditions of pressure: 20 kgf / cm ² and 220 ° C. for 2 hours is the peel strength before the heat press. The carrier had a peel strength of 2 N / m or more and 30 N / m or less after being hot-pressed under the conditions of pressure: 20 kgf / cm ² and 220 ° C. for 2 hours.
In each of Comparative Examples 1 to 16, the carrier peel strength after hot pressing the carrier-attached copper foil under the conditions of pressure: 20 kgf / cm ² and 220 ° C. for 2 hours is the peel strength before the hot press. The carrier had a peel strength of less than 2 N / m or more than 30 N / m after heat-pressing under conditions of exceeding 150% or pressure: 20 kgf / cm ² and 220 ° C. for 2 hours.

Claims (31)

A copper foil with a carrier provided with a carrier, an intermediate layer, and an ultrathin copper layer in this order,
The peel strength of the carrier after heat-pressing the copper foil with carrier under pressure: 20 kgf / cm ² and 220 ° C. for 2 hours is 150% or less of the peel strength before the heat press, A copper foil with a carrier, wherein the carrier has a peel strength of 2 N / m or more and 30 N / m or less after being hot-pressed under the conditions of 20 kgf / cm ² and 220 ° C. for 2 hours. The peel strength of the carrier after heat-pressing the copper foil with carrier under pressure: 20 kgf / cm ² and 220 ° C. for 2 hours is 150% or less of the peel strength before the heat press, The copper foil with a carrier according to claim 1, wherein the carrier has a peel strength of 5 N / m or more and 30 N / m or less after being hot-pressed at 20 kgf / cm ² and 220 ° C for 2 hours. The peel strength of the carrier after heat-pressing the copper foil with carrier under pressure: 20 kgf / cm ² and 220 ° C. for 2 hours is 150% or less of the peel strength before the heat press, The copper foil with a carrier according to claim 2, wherein the carrier has a peel strength of 5 N / m or more and 25 N / m or less after being hot-pressed at 20 kgf / cm ² and 220 ° C for 2 hours. The peel strength of the carrier after heat-pressing the copper foil with carrier under pressure: 20 kgf / cm ² and 220 ° C. for 2 hours is 150% or less of the peel strength before the heat press, The copper foil with a carrier according to claim 3, wherein the carrier has a peel strength of 5 N / m or more and 20 N / m or less after being hot-pressed at 20 kgf / cm ² and 220 ° C. for 2 hours. The carrier peel strength after heat-pressing the copper foil with carrier under pressure: 20 kgf / cm ² and 220 ° C. for 2 hours is 50 to 150% of the peel strength before the heat press. The copper foil with a carrier as described in any one of claim | item 1 -4.   The thickness of the said carrier is 5-70 micrometers, Copper foil with a carrier as described in any one of Claims 1-5.   The copper foil with a carrier as described in any one of Claims 1-6 which has a roughening process layer in any one or both of the said ultrathin copper layer side surface and the said carrier side surface.   The roughening layer is made of any single element selected from the group consisting of copper, nickel, phosphorus, tungsten, arsenic, molybdenum, chromium, iron, vanadium, cobalt, and zinc, or an alloy containing one or more of them. The copper foil with a carrier according to claim 7 which is a layer.   The copper with a carrier according to claim 7 or 8, comprising at least one layer selected from the group consisting of a heat-resistant layer, a rust-proof layer, a chromate-treated layer, and a silane coupling-treated layer on the surface of the roughened layer. Foil.   In the surface of the said ultra-thin copper layer, it has 1 or more types of layers selected from the group which consists of a heat-resistant layer, a rust prevention layer, a chromate treatment layer, and a silane coupling treatment layer. The copper foil with a carrier of description.   The copper foil with a carrier as described in any one of Claims 1-9 provided with a resin layer on the said ultra-thin copper layer.   The copper foil with a carrier according to claim 7 or 8, comprising a resin layer on the roughening treatment layer.   The copper foil with a carrier according to claim 9 or 10, comprising a resin layer on one or more layers selected from the group consisting of the heat-resistant layer, the rust-proof layer, the chromate-treated layer, and the silane coupling-treated layer.   The copper foil with a carrier as described in any one of Claims 1-13 which has an intermediate | middle layer and an ultra-thin copper layer in this order on the surface of both the said carriers.   The copper clad laminated board which used the copper foil with a carrier as described in any one of Claims 1-14 as a material.   The printed wiring board which used the copper foil with a carrier as described in any one of Claims 1-14 as a material.   An electronic device having the printed wiring board according to claim 16.   The laminated body which used the copper foil with a carrier as described in any one of Claims 1-14 as a material.   It is a laminated body containing the copper foil with a carrier and resin as described in any one of Claims 1-14, Comprising: The laminated body by which one part or all part of the end surface of the said copper foil with a carrier is covered with the said resin. .   The copper foil with a carrier according to any one of claims 1 to 14 is attached to the carrier according to any one of claims 1 to 14 from the carrier side or the ultrathin copper layer side. The laminated body laminated | stacked on the said carrier side or the said ultra-thin copper layer side of copper foil.   The carrier side surface or the ultrathin copper layer side surface of the one copper foil with carrier and the carrier side surface or the ultrathin copper layer side surface of the other copper foil with carrier are bonded as necessary. The laminate according to claim 20, wherein the laminate is directly laminated via an agent.   The laminated body according to claim 20, wherein the carrier or the ultrathin copper layer of the one copper foil with carrier and the carrier or the ultrathin copper layer of the other copper foil with carrier are joined.   The laminated body as described in any one of Claims 20-22 by which one part or all part of the end surface of the said laminated body is covered with resin.   The manufacturing method of copper foil with a carrier including the process of annealing for 5 minutes-5 hours at 160-220 degreeC with respect to copper foil with a carrier provided with the carrier, the intermediate | middle layer, and the ultra-thin copper layer in this order.   The method for producing a copper foil with a carrier according to claim 24, wherein the annealing treatment is performed at 170 to 190 ° C for 1 to 2 hours.   The manufacturing method of a copper clad laminated board including the process of bonding together the copper foil with a carrier produced by the method of Claim 24 or 25, and an insulated substrate. A step of preparing the carrier-attached copper foil according to any one of claims 1 to 14 and an insulating substrate,
A step of laminating the copper foil with carrier and an insulating substrate; and
After laminating the carrier-attached copper foil and the insulating substrate, forming a copper-clad laminate through a step of peeling the carrier of the carrier-attached copper foil,
Then, the manufacturing method of a printed wiring board including the process of forming a circuit by any method of a semi-additive method, a subtractive method, a partly additive method, or a modified semi-additive method. Forming a circuit on the ultrathin copper layer side surface or the carrier side surface of the carrier-attached copper foil according to any one of claims 1 to 14;
Forming a resin layer on the ultrathin copper layer side surface or the carrier side surface of the copper foil with carrier so that the circuit is buried;
After forming the resin layer, the step of peeling the carrier or the ultrathin copper layer, and
After the carrier or the ultra-thin copper layer is peeled off, the ultra-thin copper layer or the carrier is removed to be buried in the resin layer formed on the ultra-thin copper layer-side surface or the carrier-side surface. A method of manufacturing a printed wiring board including a step of exposing a circuit that is connected. Forming a circuit on the ultrathin copper layer side surface or the carrier side surface of the carrier-attached copper foil according to any one of claims 1 to 14;
Forming a resin layer on the ultrathin copper layer side surface or the carrier side surface of the copper foil with carrier so that the circuit is buried;
Forming a circuit on the resin layer;
After forming a circuit on the resin layer, peeling the carrier or the ultra-thin copper layer; and
After the carrier or the ultra-thin copper layer is peeled off, the ultra-thin copper layer or the carrier is removed to be buried in the resin layer formed on the ultra-thin copper layer-side surface or the carrier-side surface. A method of manufacturing a printed wiring board including a step of exposing a circuit that is connected. The step of laminating the ultrathin copper layer side surface or the carrier side surface of the copper foil with a carrier according to any one of claims 1 to 14 and a resin substrate,
A step of providing at least once two layers of a resin layer and a circuit on the surface of the ultrathin copper layer on the side opposite to the side laminated with the resin substrate of the copper foil with carrier or on the surface of the carrier; and
A method for producing a printed wiring board, comprising: a step of peeling the carrier or the ultrathin copper layer from the copper foil with a carrier after forming the resin layer and the two layers of the circuit. The step of laminating the carrier side surface of the copper foil with a carrier according to any one of claims 1 to 14 and a resin substrate,
A step of providing two layers of a resin layer and a circuit at least once on the surface of the ultrathin copper layer side opposite to the side laminated with the resin substrate of the copper foil with carrier, and
A method for producing a printed wiring board, comprising the step of peeling the ultrathin copper layer from the copper foil with a carrier after forming the resin layer and the two layers of the circuit.